Flexible crosslinked cable insulation and methods for making flexible crosslinked cable insulation

ABSTRACT

Crosslinkable polymeric compositions comprising (a) 10 to 89 weight percent of an ethylene-based interpolymer having the following properties: (i) a density of 0.93 g/cm3 or less, (ii) a high-shear viscosity (V100) at 190 C and 10% strain of 1,200 Pa·s or less, (iii) a shear thinning ratio (V0.1/V100) at 190 C and 10% strain of at least 8, and (iv) a melt index (I 2 ) greater than 1 g/10 minutes; and (b) 10 to less than 90 weight percent of a filler, where the ethylene-based interpolymer is not prepared in a high-pressure reactor. Such crosslinkable polymeric compositions may be employed as insulation layers in flexible power cables.

REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. Provisional Application No. 62/213,153, filed on Sep. 2, 2015.

FIELD

Various embodiments of the present invention relate to crosslinkable polymeric compositions for making flexible crosslinked cable insulation.

INTRODUCTION

The crosslinked insulation layer of flexible power cables is generally made of compounds comprising ethylene/propylene (“EP”) or ethylene/propylene/diene monomer (“EPDM”) polymers. These EP and EPDM interpolymers typically have a relatively high melt viscosity (e.g., as evidenced by a relatively low melt index, such as an 12 of 1 g/10 minutes or less). Such interpolymers require fillers, such as calcined clay, to assure adequate pellet stability and melt strength (or zero shear viscosity or extensional viscosity) for sag resistance during extrusion. However, the high melt viscosity and filler content of these polymers reduces the speed at which they can be extruded during cable manufacturing. Furthermore, the incorporation of filler increases the density of the insulation composition, which not only increases the mass of the fabricated cable but also may result in increased manufacturing cost of the cable. Accordingly, improvements are desired.

SUMMARY

One embodiment is a crosslinkable polymeric composition comprising:

-   -   (a) 10 to 89 weight percent, based on the total weight of said         crosslinkable polymeric composition, of an ethylene-based         interpolymer having the following properties:         -   (i) a density of 0.93 g/cm³ or less,         -   (ii) a high-shear viscosity (V100) at 190° C. and 10% strain             of 1,200 Pa·s or less,         -   (iii) a shear thinning ratio (V0.1/V100) at 190° C. and 10%             strain of at least 8, and         -   (iv) a melt index (I₂) greater than 1 g/10 minutes; and     -   (b) 10 to less than 90 weight percent, based on the total weight         of said crosslinkable polymeric composition, of a filler; and     -   wherein said ethylene-based interpolymer is not prepared in a         high-pressure reactor or process.

DETAILED DESCRIPTION

Various embodiments of the present invention concern crosslinkable polymeric compositions comprising an ethylene-based interpolymer. Additional embodiments concern crosslinked polymeric compositions prepared from such crosslinkable polymeric compositions. Further embodiments concern coated conductors incorporating the crosslinkable polymeric compositions.

Crosslinkable Polymeric Composition

As noted above, one component of the crosslinkable polymeric compositions described herein is an ethylene-based interpolymer. As used herein, “ethylene-based” interpolymers are interpolymers prepared from ethylene monomers as the primary (i.e., at least 50 weight percent (“wt %”)) monomer component, though one or more other co-monomers are employed. “Polymer” means a macromolecular compound prepared by reacting (i.e., polymerizing) monomers of the same or different type, and includes homopolymers and interpolymers. “Interpolymer” means a polymer prepared by the polymerization of at least two different monomer types. This generic term includes copolymers (usually employed to refer to polymers prepared from two different monomer types), and polymers prepared from more than two different monomer types (e.g., terpolymers (three different monomer types) and quaterpolymers (four different monomer types)).

In an embodiment, the ethylene-based interpolymer can be an ethylene/alpha-olefin (“a olefin”) interpolymer having an α-olefin content of at least 1 wt %, at least 5 wt %, at least 10 wt %, at least 15 wt %, at least 20 wt %, or at least 25 wt % based on the entire interpolymer weight. These interpolymers can have an α-olefin content of less than 50 wt %, less than 45 wt %, less than 40 wt %, or less than 35 wt % based on the entire interpolymer weight. When an α-olefin is employed, the α-olefin can be a C₃₋₂₀ (i.e., having 3 to 20 carbon atoms) linear, branched or cyclic α-olefin. Examples of C₃₋₂₀ α-olefins include propene, 1 butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1 dodecene, 1 tetradecene, 1 hexadecene, and 1-octadecene. The α-olefins can also have a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3 cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Illustrative ethylene/α-olefin interpolymers include ethylene/propylene, ethylene/1-butene, ethylene/1 hexene, ethylene/1-octene, ethylene/propylene/1-octene, ethylene/propylene/1-butene, and ethylene/1-butene/1-octene.

In various embodiments, the ethylene-based interpolymer can further comprise a non-conjugated diene comonomer. Suitable non-conjugated dienes include straight-chain, branched-chain or cyclic hydrocarbon dienes having from 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include, but are not limited to, straight-chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, and 1,9-decadiene; branched-chain acyclic dienes, such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyricene and dihydroocinene; single-ring alicyclic dienes, such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-cyclododecadiene; and multi-ring alicyclic fused and bridged-ring dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, and bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, the particularly preferred dienes are 1,4-hexadiene (“HD”), 5-ethylidene-2-norbornene (“ENB”), 5-vinylidene-2-norbornene (“VNB”), 5-methylene-2-norbornene (“MNB”), and dicyclopentadiene (“DCPD”). The most especially preferred diene is ENB. When present, the diene content of the ethylene-based interpolymer can be in the range of from 0.1 to 10.0 wt %, from 0.2 to 5.0 wt %, or from 0.3 to 3.0 wt %, based on the entire interpolymer weight.

In an embodiment, the ethylene-based interpolymer can be an ethylene/α-olefin elastomer. In various embodiments, when a diene comonomer is employed, the ethylene-based interpolymer can be an ethylene/α-olefin/diene comonomer interpolymer, such as an ethylene/propylene/diene comonomer interpolymer.

In an embodiment, the ethylene-based interpolymer can be selected from the group consisting of an ethylene/propylene copolymer, an ethylene/1-octene copolymer, an ethylene/propylene/diene comonomer terpolymer, and combinations of two or more thereof.

When the ethylene-based interpolymer is an ethylene/propylene copolymer, the ethylene can be present in the copolymer in an amount ranging from 50.0 to 98.0 wt %, and the propylene can be present in an amount ranging from 2.0 to 50.0 wt %, based on the entire interpolymer weight. When the ethylene-based interpolymer is an ethylene/1-octene copolymer, the ethylene can be present in the copolymer in an amount ranging from 50.0 to 95.0 wt %, and the 1-octene can be present in an amount ranging from 5.0 to 50.0 wt %, based on the entire interpolymer weight. When the ethylene-based interpolymer is an ethylene/propylene/diene comonomer terpolymer, the ethylene can be present in the copolymer in an amount ranging from 50.0 to 97.9 wt %, the propylene can be present in an amount ranging from 2.0 to 49.9 wt %, and the diene comonomer can be present in an amount ranging from 0.1 to 10 wt %, based on the entire interpolymer weight.

Ethylene-based interpolymers suitable for use herein have a density of 0.93 g/cm³ or less, 0.92 g/cm³ or less, 0.91 g/cm³ or less, 0.90 g/cm³ or less, or 0.89 g/cm³ or less. Additionally, ethylene-based interpolymers suitable for use herein can have a density of at least 0.85 g/cm³, at least 0.86 g/cm³, at least 0.87 g/cm³, or at least 0.88 g/cm³. Polymer densities provided herein are determined according to ASTM International (“ASTM”) method D792.

Ethylene-based interpolymers suitable for use herein have a high-shear viscosity (V100) at 100 s⁻¹, 190° C. and 10% strain of 1,200 Pa·s or less, less than 1,000 Pa·s, less than 900 Pa·s, less than 800 Pa·s, or less than 700 Pa·s. Additionally, ethylene-based interpolymers suitable for use herein can have a high-shear viscosity of at least 200 Pa·s under the same conditions. High-shear viscosity is determined according to the procedure provided in the Test Methods section, below.

Ethylene-based interpolymers suitable for use herein have a shear thinning ratio (V0.1/V100) at 190° C. and 10% strain of at least 8, at least 9, at least 10, or at least 11. Additionally, ethylene-based interpolymers suitable for use herein can have a shear thinning ratio at these conditions of less than 80, or less than 70. Shear thinning ratio is determined according to the procedure provided in the Test Methods section, below.

In an embodiment, the ethylene-based interpolymer can have a melt index (I₂) of 1.0 g/10 min. or less. In an alternate embodiment, the ethylene-based interpolymer can have a melt index (I₂) of greater than 1.0 g/10 min., at least 1.1 g/10 min., at least 1.2 g/10 min., at least 1.3 g/10 min., at least 1.4 g/10 min., or at least 1.5 g/10 min. In this embodiment, the ethylene-based interpolymer can have a melt index (I₂) of less than 10 g/10 min., less than 5 g/10 min., less than 3 g/10 min., or less than 2.5 g/10 min. In this embodiment, the ethylene-based interpolymer can have a melt index in the range of from 1.5 to 2.4 g/10 min. Melt indices provided herein are determined according to ASTM method D1238. Unless otherwise noted, melt indices are determined at 190° C. and 2.16 Kg (i.e., 12).

Ethylene-based interpolymers suitable for use herein can have a polydispersity index (“PDI,” or the ratio of weight-averaged molecular weight (Mw) to number-averaged molecular weight (Mn)) in the range of from 1 to 15, from 1.5 to 11, from 2 to 5, or from 2.5 to 4.3. PDI is determined by gel permeation chromatography according to the procedure provided in the Test Methods section, below.

Ethylene-based interpolymers suitable for use herein can have a melt discharge temperature while being extruded on a 2.5-inch 24:1 L/D extruder using a Maddock screw and 20/40/60/20 mesh screens (at set temperatures of 115.6° C. across all five zones, head and the die) at a screw speed of 100 rpm of less than 190° C., less than 180° C., or less than 170° C. Melt discharge temperatures are determined according to the procedure provided in the Test Methods section, below.

Ethylene-based interpolymers suitable for use herein can have a melt strength at 190° C. in the range of from 1 to 30 centinewtons (“cN”), from 2 to 20 cN, from 3 to 10 cN, or from 3 to 5 cN. In various embodiments, such as when the ethylene-based interpolymer has a melt index of at least 1.0 g/10 min., the ethylene-based interpolymer can have a melt strength at 190° C. in the range of from 2 to 4 cN, from 3 to 4 cN, or from 3.2 to 3.8 cN. Melt strength is determined according to the procedure provided in the Test Methods section, below.

In one or more embodiments, the ethylene-based interpolymer is not prepared in a high-pressure reactor or process. As used herein, the term “high-pressure reactor” or “high-pressure process” is any reactor or process operated at a pressure of at least 5000 psi. As known to those of ordinary skill in the art, polyethylenes prepared in a high-pressure reactor or process tend to have a highly branched polymer structure, with branches found both on the polymer backbone and on the branches themselves. In contrast, the ethylene-based interpolymer described herein can be a substantially linear polymer. As used herein, the term “substantially linear” denotes a polymer having a backbone that is substituted with 0.01 to 3 long-chain branches per 1,000 carbon atoms. In some embodiments, the ethylene-based interpolymer can have a backbone that is substituted with 0.01 to 1 long-chain branches per 1,000 carbon atoms, or from 0.05 to 1 long-chain branches per 1,000 carbon atoms.

Long-chain branching is defined herein as a chain length of at least 6 carbon atoms, above which the length cannot be distinguished by ¹³C nuclear magnetic resonance (“¹³C NMR”) spectroscopy. Long-chain branches can have a length up to about the same length as the polymer backbone. Long-chain branching is determined by ¹³C NMR spectroscopy and is quantified using the method of Randall (Rev. Macromol. Chem. Phys., C29 (2&3), p. 285-297), the disclosure of which is incorporated herein by reference.

Suitable ethylene-based interpolymers include (but are not limited to) VISTALON™ 722 ethylene/propylene copolymer and VISTALON™ 1703P ethylene/propylene/diene terpolymer.

Also distinguished from the present ethylene-based interpolymers are polymers known as linear olefin polymers which have no long-chain branching. That is, a “linear olefin polymer” has an absence of long-chain branching, as for example the traditional linear-low-density polyethylene or linear-high-density polyethylene polymers made using Ziegler polymerization processes (e.g., as taught in U.S. Pat. Nos. 4,076,698 and 3,645,992).

Suitable processes useful in producing the ethylene-based interpolymers, including the use of use of multiple loop reactors, operating in series, and a variety of suitable operating conditions for use therewith, may be found, for example, in U.S. Pat. Nos. 5,977,251, 6,545,088, 6,319,989, and 6,683,149. In particular, the polymerization is carried out as a continuous polymerization, preferably a continuous solution polymerization, in which catalyst components, monomers, and optionally solvent, adjuvants, scavengers, and polymerization aids are continuously supplied to one or more reactors or zones and polymer product continuously removed therefrom. Within the scope of the terms “continuous” and “continuously” as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular or irregular intervals so that, over time, the overall process is substantially continuous. Due to the difference in monomers, temperatures, pressures or other differences in polymerization conditions between at least two of the reactors or zones connected in series, polymer segments of differing composition such as comonomer content, crystallinity, density, tacticity, regio-regularity, or other chemical or physical difference within the same molecule are formed in the different reactors or zones.

Each reactor in the series can be operated under solution, slurry, or gas-phase polymerization conditions. In a multiple-zone polymerization, all zones operate under the same type of polymerization, such as solution, slurry, or gas phase, but at different process conditions. For a solution polymerization process, it is desirable to employ homogeneous dispersions of the catalyst components in a liquid diluent in which the polymer is soluble under the polymerization conditions employed. One such process utilizing an extremely fine silica or similar dispersing agent to produce such a homogeneous catalyst dispersion wherein normally either the metal complex or the cocatalyst is only poorly soluble is disclosed in U.S. Pat. No. 5,783,512. A slurry process typically uses an inert hydrocarbon diluent and temperatures of from 0° C. up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. Preferred temperatures in a slurry polymerization are from 30° C., preferably from 60° C. up to 115° C., preferably up to 100° C. Pressures typically range from atmospheric (100 kPa) to 500 psi (3.4 MPa). In an embodiment, the ethylene-based interpolymer is prepared using solution polymerization.

In all of the foregoing processes, continuous or substantially continuous polymerization conditions can be employed. The use of such polymerization conditions, especially continuous, solution polymerization processes, allows the use of elevated reactor temperatures which results in economical production and efficiencies.

The catalyst may be prepared as a homogeneous composition by addition of the requisite metal complex or multiple complexes to a solvent in which the polymerization will be conducted or in a diluent compatible with the ultimate reaction mixture. The desired cocatalyst or activator and may be combined with the catalyst composition either prior to, simultaneously with, or after combination of the catalyst with the monomers to be polymerized and any additional reaction diluent. The catalyst may be a Ziegler Natta catalyst.

At all times, the individual ingredients as well as any active catalyst composition must be protected from oxygen, moisture and other catalyst poisons. Therefore, the catalyst components, shuttling agent and activated catalysts must be prepared and stored in an oxygen- and moisture-free atmosphere, preferably under a dry, inert gas such as nitrogen.

An exemplary polymerization process for producing the ethylene-based interpolymer is as follows. In one or more well stirred tank or loop reactors operating under solution polymerization conditions, the monomers to be polymerized are introduced continuously together with any solvent or diluent at one part of the reactor. The reactor contains a relatively homogeneous liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C₄₋₁₀ hydrocarbons or mixtures thereof, especially alkanes such as hexane or mixtures of alkanes, as well as one or more of the monomers employed in the polymerization.

Catalyst and cocatalyst are continuously or intermittently introduced in the reactor liquid phase or any recycled portion thereof at a minimum of one location. The reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by use of cooling or heating coils, jackets or both. The polymerization rate is controlled by the rate of catalyst addition. The content of a given monomer in the polymer product is influenced by the ratio of monomers in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. The polymer product molecular weight is controlled, optionally, by controlling other polymerization variables such as the temperature, monomer concentration, or a chain-terminating agent such as hydrogen, as is well known in the art. Connected to the discharge of the reactor, optionally by means of a conduit or other transfer means, is a second reactor, such that the reaction mixture prepared in the first reactor is discharged to the second reactor without substantial termination of polymer growth. Between the first and second reactors, a differential in at least one process condition is established. Preferably for use in formation of an interpolymer of two or more monomers, the difference is the presence or absence of one or more comonomers or a difference in comonomer concentration. Additional reactors, each arranged in a manner similar to the second reactor in the series may be provided as well. Upon exiting the last reactor of the series, the effluent is contacted with a catalyst kill agent such as water, steam, or an alcohol or with a coupling agent.

The resulting polymer product is recovered by flashing off volatile components of the reaction mixture such as residual monomers or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a devolatilizing extruder. In a continuous process, the mean residence time of the catalyst and polymer in the reactor generally is from 5 minutes to 8 hours, or from 10 minutes to 6 hours.

Alternatively, the foregoing polymerization may be carried out in a plug flow reactor with a monomer, catalyst, shuttling agent, temperature or other gradient established between differing zones or regions thereof, optionally accompanied by separated addition of catalysts and/or chain shuttling agent, and operating under adiabatic or non-adiabatic polymerization conditions.

The catalyst employed in preparing the ethylene-based interpolymer comprises either or both of a first catalyst (catalyst-1) and a second catalyst (catalyst-2) in combination with a cocatalyst. Catalyst-1 can be bis((2-oxoyl-3-(9H-carbazol-9-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene-1,2-cyclohexanediylzirconium (IV) dimethyl, which is represented as the following formula:

Catalyst-1 can be prepared using the process described in U.S. Patent Publication No. 2009/0299116, which is incorporated herein by reference.

Catalyst-2 can be bis((2-oxoyl-3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2-phenoxymethyl)-methylene-1,2-cyclohexanediylzirconium (IV) dimethyl, which is represented by the following formula:

Catalyst-2 can be prepared by the procedure provided in the Materials section, below.

The cocatalyst employed can be a modified methylaluminoxane (“MMAO”), including those dissolved in solvents such as heptanes or toluene.

The ethylene-based interpolymer can be present in the crosslinkable polymeric composition in an amount ranging from 10 to 99 wt %, from 10 to 89 wt %, from 20 to 89 wt %, from 30 to 89 wt %, from 40 to 89 wt %, from 50 to 89 wt %, from 60 to 89 wt %, from 70 to 89 wt %, or from 80 to 89 wt %, based on the entire weight of the crosslinkable polymeric composition. In other embodiments, such as when little or no filler is present (as described below), the ethylene-based interpolymer can be present in the crosslinkable polymeric composition in an amount ranging from 10 to 99 wt %, from 20 to 99 wt %, from 30 to 99 wt %, from 40 to 99 wt %, from 50 to 99 wt %, from 60 to 99 wt %, from 70 to 99 wt %, from 80 to 99 wt %, or from 90 to 99 wt %, based on the entire weight of the crosslinkable polymeric composition.

As noted above, the polymeric compositions described herein are crosslinkable. The term “crosslinkable” means that the polymeric composition contains one or more additives or modifications that enhance the ethylene-based interpolymer's ability to cros slink when subjected to crosslinking conditions (e.g., heat, irradiation, or moisture). In one or more embodiments, the ethylene-based interpolymer can be rendered crosslinkable by further comprising an organic peroxide. Organic peroxides suitable for use herein include mono-functional peroxides and di-functional peroxides. As used herein, “mono-functional peroxides” denote peroxides having a single pair of covalently bonded oxygen atoms (e.g., having a structure R—O—O—R). As used herein, “di-functional peroxides” denote peroxides having two pairs of covalently bonded oxygen atoms (e.g., having a structure R—O—O—R—O—O—R). In an embodiment, the organic peroxide is a mono-functional peroxide.

Exemplary organic peroxides include dicumyl peroxide (“DCP”); tert-butyl peroxybenzoate; di-tert-amyl peroxide (“DTAP”); bis(t-butyl-peroxy isopropyl) benzene (“BIM”); isopropylcumyl t-butyl peroxide; t-butylcumylperoxide; di-t-butyl peroxide; 2,5-bis(t-butylperoxy)-2,5-dimethylhexane; 2,5-bis(t-butylperoxy)-2,5-dimethylhexyne-3; 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane; isopropylcumyl cumylperoxide; butyl 4,4-di(tert-butylperoxy)valerate; di(isopropylcumyl) peroxide; and mixtures of two or more thereof. In various embodiments, only a single type of organic peroxide is employed. In an embodiment, the organic peroxide is dicumyl peroxide.

In various embodiments, the organic peroxide can be present in the crosslinkable polymeric composition in an amount of at least 0.5 wt %, or in the range of from 0.5 to 5 wt %, from 0.5 to 3 wt %, from 0.5 to 2.5 wt %, from 1 to 2.5 wt %, or from 1.5 to 2.5 wt %, based on the entire weight of the crosslinkable polymeric composition.

As an alternative, or in addition, to the use of peroxides to render the ethylene-based interpolymer crosslinkable, other approaches for crosslinking of polymers may be used to effect the desired degree of crosslinking. Such approaches and technologies are well known to those skilled in the art and include (but are not limited to) radiation crosslinking, moisture crosslinking, bisulfonyl azide crosslinking, crosslinking with hydroxyl terminated polydimethylsiloxane, etc.

In some cases, it would be necessary for the above-described ethylene-based interpolymer to be functionalized appropriately to enable crosslinking (for example, with alkoxy silanes in the case of moisture crosslinking or crosslinking with hydroxyl terminated polydimethylsiloxane).

In various embodiments, the ethylene-based interpolymer may be rendered crosslinkable by functionalization with a hydrolyzable silane group. As known in the art, when in the presence of water, such hydrolyzable silane groups will undergo a hydrolysis reaction to generate Si—O—Si bonds to form a crosslinking network between polymer chains (a.k.a., moisture crosslinking or moisture curing). Functionalization of the ethylene-based interpolymer can be accomplished by either copolymerizing a monomer having a hydrolyzable silane group with the above-described ethylene and comonomers or by grafting a hydrolyzable silane group to the backbone of the ethylene-based interpolymer in a post-reactor process. Such techniques are within the capabilities of one having ordinary skill in the art.

Hydrolyzable silane monomers suitable for use in forming a silane-functionalized ethylene-based interpolymer can be any hydrolyzable silane monomer that will effectively copolymerize with an olefin (e.g., ethylene), or graft to and crosslink an olefin (e.g., ethylene) polymer. Those described by the following formula are exemplary:

in which R′ is a hydrogen atom or methyl group; x is 0 or 1; n is an integer from 1 to 12 inclusive, preferably 1 to 4, and each R″ independently is a hydrolyzable organic group such as an alkoxy group having from 1 to 12 carbon atoms (e.g. methoxy, ethoxy, butoxy), an aryloxy group (e.g. phenoxy), an araloxy group (e.g. benzyloxy), an aliphatic acyloxy group having from 1 to 12 carbon atoms (e.g. formyloxy, acetyloxy, propanoyloxy), an amino or substituted amino group (alkylamino, arylamino), or a lower-alkyl group having 1 to 6 carbon atoms inclusive, with the proviso that not more than one of the three R″ groups is an alkyl. Such silanes may be copolymerized with ethylene in a reactor, such as a high-pressure process. Such silanes may also be grafted to a suitable ethylene polymer by the use of a suitable quantity of organic peroxide. Suitable silanes include unsaturated silanes that comprise an ethylenically unsaturated hydrocarbyl group, such as a vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or gamma (meth)acryloxy allyl group, and a hydrolyzable group, such as, for example, a hydrocarbyloxy, hydrocarbonyloxy, or hydrocarbylamino group. Examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, proprionyloxy, and alkyl or arylamino groups. Preferred silanes are the unsaturated alkoxy silanes which can be grafted onto the polymer or copolymerized in-reactor with other monomers (such as ethylene and acrylates). These silanes and their method of preparation are more fully described in U.S. Pat. No. 5,266,627 to Meverden, et al. Suitable hydrolyzable silane monomers include, but are not limited to, vinyltrimethoxysilane (“VTMS”), vinyltriethoxysilane (“VTES”), vinyltriacetoxysilane, and gamma-(meth)acryloxy propyl trimethoxy silane. When included, the silane functional comonomer can constitute in the range of from 0.2 to 10 wt % of the ethylene-based interpolymer.

In one or more embodiments, the crosslinkable polymeric composition may optionally comprise a filler. Fillers suitable for use herein include, but are not limited to, heat-treated clay, surface-treated clay, organo-clay, precipitated silica and silicates, fumed silica, calcium carbonate, ground minerals, aluminum trihydroxide, magnesium hydroxide, and carbon blacks.

In certain embodiments, the crosslinkable polymeric composition comprises 0 to less than 10 wt % filler, based on the entire weight of the crosslinkable polymeric composition. Additionally, the crosslinkable polymeric composition can comprise less than 8 wt %, less than 5 wt %, less than 2 wt %, or less than 1 wt % filler, based on the entire weight of the crosslinkable polymeric composition. In various embodiments, the crosslinkable polymeric composition can be free or substantially free of filler. As used herein with respect to filler content, the term “substantially free” denotes a concentration of less than 10 parts per million by weight, based on the entire weight of the crosslinkable polymeric composition.

In alternate embodiments, particularly when the ethylene-based interpolymer has a melt index (I₂) of greater than 1.0 g/10 min., the crosslinkable polymeric composition can comprise filler in an amount of at least 10 wt % and up to 90 wt %, based on the entire weight of the crosslinkable polymeric composition. Furthermore, in such embodiments, the filler can be present in the range of from 15 to 60 wt %, or from 15 to 35 wt %, based on the entire weight of the crosslinkable polymeric composition.

In one or more embodiments, the crosslinkable polymeric composition can optionally comprise a polyethylene prepared by a high-pressure process or reactor, such as a high-pressure low-density polyethylene (“HP LDPE”). High-pressure polyethylenes suitable for use herein can have a melt strength at 190° C. of greater than 4 cN, at least 6 cN, or at least 8 cN. Additionally, high-pressure polyethylenes suitable for use can have a melt strength at 190° C. in the range of from 4 to 30 cN, from 6 to 20 cN, or from 8 to 15 cN.

Such high-pressure polyethylenes generally have a density ranging from about 0.91 to about 0.94 g/cm³. In various embodiments, the high-pressure polyethylene is a high-pressure LDPE having a density of at least 0.915 g/cm³, but less than 0.94 or less than 0.93 g/cm³. HP LDPEs suitable for use herein can have a melt index (I₂) of less than 20 g/10 min., or ranging from 0.1 to 10 g/10 min., from 0.5 to 5 g/10 min., from 1 to 3 g/10 min., or an 12 of 2 g/10 min. Additionally, such HP LDPEs generally have a broad molecular weight distribution resulting in a high polydispersity index. When present, the high-pressure polyethylene can be present in an amount of greater than 0 but less than 80 wt %, from 10 to less than 70 wt %, from 20 to 50 wt %, or from 30 to 40 wt %, based on the total weight of the crosslinkable polymeric composition.

In one embodiment, the high-pressure polyethylene comprises ethylene and one or more comonomers, and preferably one comonomer. Comonomers include, but are not limited to, di or higher functional (meth)acrylates, monomeric chain transfer agents, acetates, alkoxy silane, a olefins, acrylates, methacrylates and anhydrides, each typically having no more than 20 carbon atoms. The α-olefin comonomers, which have a combined monomer and chain transfer agent functionality, may have 3 to 10 carbon atoms, or in the alternative, the α-olefin comonomers may have 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1 butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4 methyl-1-pentene and combinations thereof. Preferably, the α-olefin comonomers are selected from propylene, 1 butene and combinations thereof.

Suitable commercially available high-pressure polyethylenes include, but are not limited to, DFDA-1216 NT available from The Dow Chemical Company, BPD2000E available from INEOS Olefins and Polymers Europe, and LDPE 2102TX00 available from SABIC Europe.

In one or more embodiments, the crosslinkable polymeric composition can optionally comprise a propylene polymer. Propylene polymers suitable for use herein can have (but are not limited to having) an upper melting point of at least 130° C., or from 130° C. to 170° C. When present, the propylene polymer can be present in an amount of greater than 0 to less than 80 wt %, from 1 to 70 wt %, from 2 to 50 wt %, or from 3 to 30 wt %, or from 5 to 15 wt %, based on the total weight of the crosslinkable polymeric composition.

The propylene polymer useful herein can be a homopolymer or one or more copolymers of units derived from propylene and up to 30, preferably up to 20, mole percent ethylene and/or one or more other α-olefins having up to 20, preferably up to 12 and more preferably up to 8, carbon atoms. If a copolymer, it is typically random, block, or graft. The propylene polymer may be a Ziegler-Natta-catalyzed polymer, a metallocene-catalyzed polymer, or a constrained-geometry-catalyst-catalyzed polymer, and may be made using gas phase, solution, or slurry polymer manufacturing processes. The propylene polymer may be a homopolymer or a blend of a homopolymer and one or more copolymers, or a blend of two or more copolymers. “Propylene homopolymer” and similar terms mean a polymer consisting solely or essentially all of units derived from propylene.

The molecular weight of the propylene polymer is conveniently indicated using a melt flow measurement according to ASTM D1238 (condition 230° C./2.16 kg). The melt flow rate of the propylene polymer can be from about 0.1 to 100 g/10 min., from about 0.5 to 40 g/10 min., from 0.5 to 10 g/10 min., or from 1 to 5 g/10 min. Examples of propylene polymers useful herein are more fully described in Modern Plastics Encyclopedia/89, mid October 1988 Issue, Volume 65, Number 11, pp. 86-92.

The propylene polymer can be primarily isotactic or primarily syndiotactic. As here used with respect to the polypropylene homopolymer, the term “primarily” means greater than 60 percent. For example, a primarily syndiotactic polypropylene homopolymer can have greater than 60 percent racemo diads. In an embodiment, the propylene homopolymer is primarily isotactic. In various embodiments, the propylene homopolymer can have at least 70, at least 80, at least 90, or at least 95 percent isotactic pentads as determined by ¹³C NMR analysis.

In one embodiment the propylene polymer is a non-nucleated homo- or copolymer.

If the propylene polymer is a copolymer comprising one or more α-olefin comonomers, the α-olefin can be ethylene, a C4-20 (i.e., a monomer having 4 to 20 carbon atoms) linear, branched, or cyclic α-olefin, or mixtures of two or more thereof. Non-limiting examples of suitable C4-20 α-olefins include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. The α-olefins can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Illustrative propylene-α-olefin interpolymers include propylene/ethylene, propylene/butene, propylene/1-hexene, and propylene/1-octene. The propylene-α-olefin interpolymers can be random interpolymers. In one embodiment, the α-olefin component of the propylene-α-olefin interpolymer is ethylene.

The polymerized α-olefin component of the propylene-α-olefin interpolymer can constitute from greater than 0 to up to 15 mole percent (“mol %”), or from 5 to 15 mol %, of the total propylene-α-olefin interpolymer. Polymerized propylene can constitute all or substantially all of the remainder of the propylene-α-olefin interpolymer.

In one embodiment the propylene polymer can have a polydispersity index (“PDI”) (i.e., weight average molecular weight/number average molecular weight; “Mw/Mn;” or molecular weight distribution (“MWD”)) from 2 to 12, or from 3 to 8, as determined by gel permeation chromatography.

Suitable commercially available propylene polymers include, but are not limited to, BRASKEM™ FF018F and BRASKEM™ PP H358-02, both available from Braskem S.A. (Sao Paulo, Brazil); MOPLEN™ HP1073, available from LyondellBasell (Rotterdam, Netherlands); or PP525 P available from SABIC (Riyadh, Saudi Arabia).

The crosslinkable polymeric composition may also contain other additives including, but not limited to, antioxidants, crosslinking agents (e.g., cure boosters or coagents), other polymers beyond those noted above, tree-retardants (e.g., polyethylene glycol, polar polyolefin copolymers, etc.), scorch-retardants, processing aids, fillers, coupling agents, ultraviolet absorbers or stabilizers, antistatic agents, nucleating agents, slip agents, plasticizers, lubricants, viscosity control agents, tackifiers, anti-blocking agents, surfactants, extender oils, acid scavengers, flame retardants, and metal deactivators. Examples of known crosslinking coagents are triallyl isocyanurate, ethoxylated bisphenol A dimethacrylate, α-methyl styrene dimer (AMSD), and other co-agents described in U.S. Pat. Nos. 5,346,961 and 4,018,852. Additives, other than fillers, are typically used in amounts ranging from 0.01 or less to 10 or more wt % based on total composition weight.

As mentioned above, an antioxidant can be employed with the cross-linkable polymeric composition. Exemplary antioxidants include hindered phenols (e.g., tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane); phosphites and phosphonites (e.g., tris (2,4-di-t-butylphenyl) phosphate); thio compounds (e.g., dilaurylthiodipropionate); various siloxanes; and various amines (e.g., polymerized 2,2,4-trimethyl-1,2-dihydroquinoline). Antioxidants can be used in amounts of 0.1 to 5 wt % based on the total weight of the crosslinkable polymeric composition. In the formation of wire and cable compositions, discussed below, antioxidants may be added to the system before processing (i.e., prior to extrusion and crosslinking) of the finished article.

The components of the composition can be blended in any manner and using any equipment. Typically, the polymers are melted blended with one another in conventional mixing equipment, e.g., a BRABENDER™ batch mixer or extruder, to form a relatively homogeneous blend comprising continuous, co-continuous and/or discontinuous phases. The mixing or blending may be done at, below or above the upper melting temperature (point) of the polymers. The peroxide and other additives can be added in any manner, including soaking and mixing. In one embodiment, the peroxide and other additives are blended with one another and then added to one or more of the polymers or polymer blend. In one embodiment the peroxide and other additives are added individually. In one embodiment one or more of the components are mixed with one or more of the polymers before melt-blending with one another. In one embodiment one or more of the peroxide and other additives are added as a masterbatch either to the blended polymers or to one or more of the polymers prior to melt blending. Typically, the peroxide is the last component to be added to one or more of the polymers or polymer blend although here too, it can be first soaked or mixed with one or more of the polymers prior to the melt blending of the polymers. In an embodiment, all the ingredients (including peroxide) are melt-blended in one step. In another embodiment, all the ingredients (including peroxide) are melt-blended in one step as part of the cable extrusion process, without a need to first prepare a compound prior to use during cable extrusion.

For example, compounding can be performed by either (1) compounding all components into the ethylene-based interpolymer, or (2) compounding all the components except for the organic peroxide and other liquid additives, which may be soaked into the ethylene-based interpolymer composition after all others have been incorporated. Compounding can be performed at a temperature of greater than the melting temperature of the ethylene-based interpolymer up to a temperature above which the ethylene-based interpolymer begins to degrade. In various embodiments, compounding can be performed at a temperature ranging from 100 to 200° C., or from 110 to 150° C. In various embodiments, soaking the organic peroxide and/or other liquid additives into the ethylene-based interpolymer or ethylene-based interpolymer composition can be performed at a temperature ranging from 30 to 100° C., from 50 to 90° C., or from 60 to 80° C.

The resulting crosslinkable polymeric composition can have a zero-shear viscosity at 135° C. of at least 10,000 Pa·s, at least 20,000 Pa·s, or at least 30,000 Pa·s. Additionally, the crosslinkable polymeric composition can have a zero-shear viscosity at 135° C. of up to 400,000 Pa·s. Zero-shear viscosity is determined according to the procedure described in the Test Methods section, below.

The crosslinkable polymeric composition can have an extensional viscosity of greater than 300,000 Poise, greater than 350,000 Poise, or greater than 400,000 Poise when measured at 120° C. and a Hencky strain of 1. Similarly, the crosslinkable polymeric composition can have an extensional viscosity of greater than 300,000 Poise, greater than 350,000 Poise, or greater than 400,000 Poise when measured at 135° C. and a Hencky strain of 1. Regardless of whether measured at 120° C. or 135° C., the crosslinkable polymeric composition can have an extensional viscosity up to 6,000,000 Poise at any Hencky strain. Extensional viscosity is determined according to the procedure described in the Test Methods section, below.

The crosslinkable polymeric composition can have a time for a 1 lb-in. increase in torque (“ts1”) at 140° C. of at least 10 minutes, at least 15 minutes, or at least 20 minutes. Additionally, the crosslinkable polymeric composition can have a ts1 of up to 300 min. Determination of ts1 is done according to the procedure described in the Test Methods section, below.

Crosslinked Polymeric Composition

The above-described crosslinkable polymeric composition can be cured or allowed to cure in order to form a crosslinked polymeric composition. When a peroxide is employed, such curing can be performed by subjecting the crosslinkable polymeric composition to elevated temperatures in a heated cure zone, which can be maintained at a temperature in the range of 175 to 260° C. The heated cure zone can be heated by pressurized steam or inductively heated by pressurized nitrogen gas. Thereafter, the crosslinked polymeric composition can be cooled (e.g., to ambient temperature).

Following crosslinking, the crosslinked polymeric composition can undergo degassing to remove at least a portion of the volatile decomposition byproducts. Degassing can be performed at a degassing temperature, a degassing pressure, and for a degassing time period to produce a degassed polymeric composition. In various embodiments, the degassing temperature can range from 50 to 150° C., or from 60 to 80° C. In an embodiment, the degassing temperature is 65 to 75° C. Degassing can be conducted under standard atmosphere pressure (i.e., 101,325 Pa).

The extent of crosslinking in the crosslinked polymeric composition can be determined via analysis on a moving die rheometer (“MDR”) at 182° C. according to ASTM D5289. Upon analysis, an increase in torque, as indicated by the difference between the maximum torque (“MH”) and the minimum torque (“ML”) (“MH-ML”), indicates greater degree of crosslinking. In various embodiments, the resulting crosslinked polymeric composition can have an MH-ML of at least 0.2 lb-in., at least 0.6 lb-in., at least 1.0 lb-in., at least 1.4 lb-in., at least 1.8 lb-in., or at least 2.0 lb-in. Additionally, the crosslinked polymeric composition can have an MH-ML up to 30 lb-in.

In various embodiments, the crosslinked polymeric composition can have a Shore D hardness of 40 or less, 35 or less, or 30 or less. Additionally, the crosslinked polymeric composition can have a Shore D hardness of at least 10. In one or more embodiments, the crosslinked polymeric composition can have a Shore A hardness of 93 or less, 90 or less, or 85 or less. Additionally, the crosslinked polymeric composition can have a Shore A hardness of at least 60. Shore A and D hardness are determined according to ASTM D2240.

In one or more embodiments, the crosslinkable polymeric composition can have a gel content of at least 30 wt %, at least 40 wt %, or at least 50 wt %. Additionally, the crosslinkable polymeric composition can have a gel content up to 99 wt %. Gel content is determined according to ASTM D2765.

In various embodiments, the crosslinked polymeric composition can have a hot creep of any value, even if not measurable due to insufficient crosslinking for hot creep to be measurable. In other embodiments, the crosslinked polymeric composition can have a hot creep value of 200% or less, 150% or less, 75% or less, 50% less, or 25% or less. Hot creep is determined according to the standard method ICEA-T-28-562:2003.

In one or more embodiments, the crosslinked polymeric composition can have a dissipation factor of less than 10%, less than 4%, less than 1%, or less than 0.5% when measured at 60 Hz, 2 kV, and 130° C. Dissipation factor is determined according to ASTM D150.

Coated Conductor

A cable comprising a conductor and an insulation layer can be prepared employing the above-described crosslinkable polymeric composition. The above-described crosslinkable polymeric composition may be used to make one or more layers of the coated conductor (including insulation, semiconductive shield, and jacket). “Cable” and “power cable” mean at least one wire or optical fiber within a sheath, e.g., an insulation covering or a protective outer jacket. Typically, a cable is two or more wires or optical fibers bound together, typically in a common insulation covering and/or protective jacket. The individual wires or fibers inside the sheath may be bare, covered or insulated. Combination cables may contain both electrical wires and optical fibers. Typical cable designs are illustrated in U.S. Pat. Nos. 5,246,783, 6,496,629 and 6,714,707. “Conductor” denotes one or more wire(s) or fiber(s) for conducting heat, light, and/or electricity. The conductor may be a single-wire/fiber or a multi-wire/fiber and may be in strand form or in tubular form. Non-limiting examples of suitable conductors include metals such as silver, gold, copper, carbon, and aluminum. The conductor may also be optical fiber made from either glass or plastic.

Such a cable can be prepared with various types of extruders (e.g., single or twin screw types) by extruding the crosslinkable polymeric composition onto the conductor, either directly or onto an interceding layer. A description of a conventional extruder can be found in U.S. Pat. No. 4,857,600. An example of co-extrusion and an extruder therefore can be found in U.S. Pat. No. 5,575,965. Following extrusion, the extruded cable can pass into a heated cure zone downstream of the extrusion die to aid in crosslinking the crosslinkable polymeric composition and thereby produce a crosslinked polymeric composition. The heated cure zone can be maintained at a temperature in the range of 175 to 260° C. In an embodiment, the heated cure zone is a continuous vulcanization (“CV”) tube. In various embodiments, the crosslinked polymeric composition can then be cooled and degassed, as discussed above.

Alternating current cables prepared according to the present disclosure can be low voltage, medium voltage, high voltage, or extra-high voltage cables. Further, direct current cables prepared according to the present disclosure include high or extra-high voltage cables.

Test Methods

Density

Density is determined according to ASTM D792.

Melt Index

Melt index, or 12, is measured in accordance with ASTM D1238, condition 190° C./2.16 kg, and is reported in grams eluted per 10 minutes. The I₁₀ is measured in accordance with ASTM D1238, condition 190° C./10 kg, and is reported in grams eluted per 10 minutes.

Molecular Weight Distribution

A high-temperature gel permeation chromatography (“GPC”) system is employed, equipped with Robotic Assistant Deliver (“RAD”) system for sample preparation and sample injection. The concentration detector is an Infra-red detector (IR4) from Polymer Char Inc. (Valencia, Spain). Data collection is performed using Polymer Char DM 100 Data acquisition box. The carrier solvent is 1,2,4-trichlorobenzene (“TCB”). The system is equipped with an on-line solvent degas device from Agilent. The column compartment is operated at 150° C. The columns are four Mixed A LS 30-cm, 20-micron columns. The solvent is nitrogen-purged TCB containing approximately 200 ppm 2,6-di-t-butyl-4-methylphenol (“BHT”). The flow rate is 1.0 mL/min, and the injection volume is 200 μl. A 2 mg/mL sample concentration is prepared by dissolving the sample in nitrogen-purged and preheated TCB (containing 200 ppm BHT) for 2.5 hours at 160° C. with gentle agitation.

The GPC column set is calibrated by running twenty narrow molecular weight distribution polystyrene (“PS”) standards. The molecular weight (“MW”) of the standards ranges from 580 to 8,400,000 g/mol, and the standards are contained in six “cocktail” mixtures. Each standard mixture has at least a decade of separation between individual molecular weights. The equivalent polypropylene (“PP”) molecular weights of each PS standard are calculated by using the following equation, with reported Mark-Houwink coefficients for polypropylene (Th.G. Scholte, N. L. J. Meijerink, H. M. Schoffeleers, and A. M. G. Brands, J. Appl. Polym. Sci., 29, 3763-3782 (1984)) and polystyrene (E. P. Otocka, R. J. Roe, N.Y. Hellman, P. M. Muglia, Macromolecules, 4, 507 (1971)):

$\begin{matrix} {{M_{PP} = \left( \frac{K_{PS}M_{ss}^{a_{ps} + 1}}{K_{PP}} \right)^{\frac{1}{a_{pp} + 1}}},} & (1) \end{matrix}$ where M_(PP) is PP equivalent MW, M_(PS) is PS equivalent MW, log K and a values of Mark-Houwink coefficients for PP and PS are listed below.

Polymer a log K Polypropylene 0.725 −3.721 Polystyrene 0.702 −3.900

A logarithmic molecular weight calibration is generated using a fourth order polynomial fit as a function of elution volume. Number average and weight average molecular weights are calculated according to the following equations:

$\begin{matrix} {{{Mn} = \frac{\sum\limits^{i}\;{Wf}_{i}}{\sum\limits^{i}\;\left( {{Wf}_{i}/M_{i}} \right)}},} & (2) \\ {{{Mw} = \frac{\sum\limits^{i}\;\left( {{Wf}_{i}*M_{i}} \right)}{\sum\limits^{i}\;{Wf}_{i}}},} & (3) \end{matrix}$ where Wf_(i) and M_(i) are the weight fraction and molecular weight of elution component i, respectively. Extrusion Evaluation

Extrusion evaluation of the polymers (including ethylene-based interpolymers alone or HP LDPE alone) is conducted on a 2.5-inch 24:1 L/D extruder using a Maddock screw and 20/40/60/20 mesh screens (at set temperatures of 115.6° C. across all five zones, head and the die). The screw speeds range from 25 rpm to 100 rpm. Melt discharge temperature is measured by immersing the probe of a hand-held thermocouple (pyrometer) in the molten polymer as it exits the die. This parameter is a measure of the extent of shear-heating prevalent.

Shear Viscosity

To determine the melt-flow properties of the ethylene-based interpolymers alone or HP LDPE alone, dynamic oscillatory shear measurements are conducted over a range of 0.1 rad s⁻¹ to 100 rad s⁻¹ at a temperature of 135° C. or 190° C. and 10% strain with stainless steel parallel plates of 25-mm diameter on the strain-controlled rheometer ARES/ARES-G2 by TA Instruments. V0.1 and V100 are the viscosities at 0.1 and 100 rad s⁻¹, respectively, with V0.1/V100 being a measure of shear thinning characteristics.

To determine the melt-flow properties of the full crosslinkable polymeric compositions (including peroxide-containing compositions), dynamic oscillatory shear measurements are conducted over a range of 0.1 rad s⁻¹ to 100 rad s⁻¹ using a TA Instruments Advanced Rheometric Expansion System at a temperature of 120° C. or 135° C. and 0.25% strain. V0.1 and V100 are the viscosities at 0.1 and 100 rad s⁻¹, respectively, with V0.1/V100 being a measure of shear thinning characteristics.

Extensional Viscosity

Extensional viscosity is measured using an ARES FCU Rheometer with Extensional Viscosity Fixture Geometry and TA Orchestrator software on full crosslinkable polymeric compositions (including peroxide-containing compositions). The test is conducted at a rate of 1/sec at 120° C. or 135° C. to simulate extrusion conditions. The maximum (“peak”) value of viscosity attained is reported, as well as the viscosity at Hencky Strain of 1 and the maximum Hencky strain.

Zero Shear Viscosity

Zero shear viscosity is measured from creep recovery (SR-200, 25.0 Pa/3 minutes creep/15 minutes recovery/135° C.) on ethylene-based interpolymers alone or HP LDPE alone or full crosslinkable polymeric compositions (including peroxide-containing compositions).

Moving Die Rheometer

Moving Die Rheometer (“MDR”) analyses are performed on the compounds using Alpha Technologies Rheometer MDR model 2000 unit. Testing is based on ASTM procedure D5289. The MDR analyses are performed using 6 grams of material. Samples are tested at 182° C. or at 140° C. at 0.5 degrees arc oscillation for both temperature conditions. Samples are tested on material directly from the Brabender mixing bowl. Resistance to premature crosslinking at extrusion conditions (“scorch”) is assessed by ts1 (time for 1 lb-in increase in elastic torque) at 140° C. Ultimate degree of crosslinking is reflected by MH (maximum elastic torque)—ML (minimum elastic torque) at 182° C.

Gel Content

Gel content (insoluble fraction) is determined by extracting with decahydronaphthalene (decalin) according to ASTM D2765. The test is conducted on specimens resulting from MDR experiments at 182° C. A WILEY mill is used (20-mesh screen) to prepare powdered samples, at least one gram of material for each sample. Fabrication of the sample pouches is crafted carefully to avoid leaks of the powdered samples from the pouch. In any technique used, losses of powder to leaks around the folds or through staple holes are to be avoided. The width of the finished pouch is no more than three quarters of an inch, and the length is no more than two inches. 120 mesh screens are used for pouches. The sample pouch is weighed on an analytical balance. 0.3 grams (+/−0.02 g) of powdered samples is placed into the pouch. Since it is necessary to pack the sample into the pouch, care is given not to force open the folds in the pouch. The pouches are sealed and samples are then weighed. Samples are then placed into one liter of boiling decahydronaphthalene (decalin), with 10 grams of 2,2′-methylene-bis(4-methyl-6-tertiary butyl phenol) for 6 hours using flasks in a heated mantle. After the (decalin) has boiled for six hours, the voltage regulator is turned off leaving the cooling water running until (decalin) has cooled below its flash point (this typically takes at least a half hour). When the (decalin) has cooled, the cooling water is turned off and the pouches removed from the flasks. The pouches are allowed to cool under a hood, to remove as much solvent as possible. Then the pouches are placed in a vacuum oven set at 150° C. for four hours, maintaining a vacuum of 25 inches of mercury. The pouches are then taken out of the oven and allowed to cool to room temperature. Weights are recorded on an analytical balance. The calculation for gel extraction is shown below where W1=weight of empty pouch, W2=weight of sample and pouch, W3=weight of sample, pouch and staple, and W4=weight after extraction. % extracted=((W3−W4)/(W2−W1))×100 Gel Content=100−% extracted Hot Creep

Hot creep is determined according to ICEA-T-28-562:2003. Hot creep testing is conducted on 50-mil (1.3-mm) thick samples in an oven with a glass door at 150° C. or 200° C. with 0.2 MPa stress applied to the bottom of the specimens. Three test specimens for each sample are cut using ASTM D412 type D tensile bars. The samples are elongated for 15 minutes where the percentage increases in length are measured and the average values of the three specimens are reported.

Dissipation Factor

Dissipation factor (“DF”) testing at 60 Hz and 2 kV applied voltage is conducted on crosslinked 50-mil (1.3-mm) plaques. The plaques are degassed in a vacuum oven at 60° C. for five days. DF testing is carried out according to ASTM D150 at 60 Hz on a GUILDLINE High Voltage Capacitance Bridge unit, Model 9920A, with a TETTEX specimen holder and a TETTEX AG Instruments Temperature Control Unit. Samples are tested at 60 Hz and 2 kV applied voltage at temperatures of 25° C., 40° C., 90° C., and 130° C.

AC Breakdown Strength

AC breakdown strength (“ACBD”), also known as AC dielectric strength, is tested with nominal 35-mil (0.9-mm) thick cured plaques on a BRINKMAN AC Dielectric Strength Tester using EXXON Univolt N61 transformer oil. Aged samples are aged in a glass U-tube filled with 0.01 M sodium chloride solution for twenty one days at 6 kV.

Shore Hardness

Determine Shore A and Shore D hardness according to ASTM D2240 on specimens of 250 mil (6.4 mm) thickness and 51 mm diameter, and record the average of five measurements.

Flexural Modulus

Flexural Modulus (2% secant modulus) is tested according to ASTM D790 with an INSTRON™ model 4201 tensile testing machine on crosslinked molded specimens with a nominal 125 mil (3.2 mm) thickness. The 3-point bend flexural modulus is conducted on a bar of rectangular cross section rested on two supports and loaded by means of a loading nose midway between the supports at 0.1 inches/minute (2.5 mm/min).

Melt Strength

Melt strength of polymers (including ethylene-based interpolymers alone or HP LDPE alone) is measured by Rheotens at 135° C. or 190° C. Melt strength, as used herein, is a maximum tensile force measured on a molten filament of a polymer melt extruded from a capillary rheometer die at a constant shear rate of 33 reciprocal seconds (sec⁻¹) while the filament is being stretched by a pair of nip rollers that are accelerating the filament at a rate of 0.24 centimeters per second per second (cm/sec²) from an initial speed of 1 cm/sec. The molten filament is preferably generated by heating 10 grams (g) of a polymer that is packed into a barrel of an Instron capillary rheometer, equilibrating the polymer at 135° C. for five minutes and then extruding the polymer at a piston speed of 2.54 cm/minute (cm/min) through a capillary die with a diameter of 0.21 cm and a length of 4.19 cm. The tensile force is preferably measured with a Goettfert Rheotens located so that the nip rollers are 10 cm directly below a point at which the filament exits the capillary die.

Materials

The following materials are employed in the Examples, below.

VISTALON™ 722 is an ethylene/propylene copolymer rubber having a melt index of 1.0 g/10 min., an ethylene content of 72.0 wt %, and a Mooney viscosity at 125° C. of 17 MU, which is commercially available from ExxonMobil Chemical Company, Houston, Tex., USA.

VISTALON™ 1703 P is an ethylene/propylene/diene terpolymer rubber having an ethylene content of 77.0 wt %, a vinyl norbornene content of 0.9 wt %, and a Mooney viscosity at 125° C. of 25 MU, which is commercially available from ExxonMobil Chemical Company, Houston, Tex., USA.

NORDEL™ IP 3722P EL is a hydrocarbon rubber (EPDM) having a density of 0.87 g/cm³, a Mooney viscosity at 125° C. of 18 MU, an ethylene content of 70.5 wt %, and an ethylidene norbornene content of 0.5 wt %, which is commercially available from The Dow Chemical Company, Midland, Mich., USA.

POE-1 is an ethylene/1-octene polyolefin elastomer having a melt index (I₂) of 3.0 g/10 min., and a density of 0.875 g/cm³, which is prepared by The Dow Chemical Company, Midland, Mich., USA.

POE-2 is an ethylene/1-octene polyolefin elastomer having a melt index (I₂) of 4.8 g/10 min., and a density of 0.872 g/cm³, which is prepared by The Dow Chemical Company, Midland, Mich., USA.

LDPE-1 is a high-pressure low-density polyethylene (HP LDPE) having a density of 0.922 g/cm³ and a melt index (I₂) of 1.8 g/10 min., which is available from The Dow Chemical Company, Midland, Mich., USA.

LDPE-2 is a second HP LDPE having a density of 0.920 g/cm³ and a melt index (I₂) of 2.3 g/10 min., which is available from The Dow Chemical Company, Midland, Mich., USA.

The polypropylene employed is BRASKEM™ FF018F, which has a nominal melt flow rate (230° C./2.16 kg) of 1.8 g/10 min. and is commercially available from Braskem America, Inc., Philadelphia, Pa., USA.

Dicumyl peroxide is commercially available under the trade name PERKADOX™ BC-FF from AkzoNobel Polymer Chemicals LLC, Chicago Ill., USA.

The polyethylene glycol is PEG 20000 (Clamant Polyglykol 20000 SRU), which is a polyethylene glycol having a mean molecular weight of 20000 and is commercially available from Clamant Corporation, Charlotte, N.C., USA.

Nofmer MSD, also known as 2,4-diphenyl-4-methyl-1-pentene or α-methyl styrene dimer (“AMSD”), is commercially available from NOF Corporation, Tokyo, Japan.

LOWINOX™ TBM-6 is an antioxidant having the chemical name 4,4′-thiobis(2-t-butyl-5-methylphenol), and is commercially available from Addivant Corporation, Danbury, Conn., USA.

CYANOX™ 2212 is a mixed lauryl-stearylthiodipropionate antioxidant available from Cytec Industries Inc., Woodland Park, N.J., USA.

SABO™ STAB UV 119 is a high-molecular-weight hindered-amine light stabilizer having as its main component 1,3,5-triazine-2,4,6-triamine, N2,N2″-1,2-ethanediylbis[N2-[[4-[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]amino]propyl]-N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-, which is commercially available from Sabo S.p.A., Bergamo, Italy.

BURGESS™ KE clay is a silane-modified anhydrous aluminum silicate having a silica (SiO₂) content of 51 to 52.4 wt %, an alumina (Al₂O₃) content of 42.1 to 44.3 wt %, a titanium dioxide content of 1.56 to 2.50 wt %, trace amounts of iron oxide (Fe₂O₃), a GE brightness of 90.0%, an average particle size sedigraph of 1.5 μm, and a specific gravity of 2.63, which is commercially available from Burgess Pigment Company, Sandersville, Ga., USA.

Translink™ 37 is a calcined and surface-treated aluminosilicate (calcined clay), commercially available from BASF North America, Florham Park, N.J.

The zinc oxide employed is KADOX™ 920, which is commercially available from Horsehead Corporation, Monaca, Pa., USA.

Polydispersion ERD 90 is Pb₃O₄ (red lead oxide), CAS #1314-41-6, available from RheinChemie Rheinau GmbH, Mannheim, Germany.

ANTILUX™ 654 is a paraffin wax available from RheinChemie Rheinau GmbH, Mannheim, Germany.

FLOWSPERSE™ PAC-473 is a silane in wax carrier, commercially available from Flow Polymers, LLC, Cleveland, Ohio, USA.

AGERITE™ MA is a polymerized 1,2-dihydro-2,2,4-trimethylquinoline, which is commercially available from Vanderbilt Chemicals, LLC, Norwalk, Conn., USA.

Catalyst-1, bis((2-oxoyl-3-(9H-carbazol-9-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene-1,2-cyclohexanediylzirconium (IV) dimethyl, is purchased from Boulder Scientific Company, Longmont, Colo., USA, and used without further purification.

Catalyst-2, bis((2-oxoyl-3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-2-phenoxymethyl)-methylene-1,2-cyclohexanediylzirconium (IV) dimethyl, is prepared according to the following procedure.

Preparation of 3,6-bis(1,1-dimethylethyl)-9H-carbazole

A 500-mL, three-necked, round-bottom flask, equipped with an overhead stirrer, nitrogen gas bubbler, and an addition funnel, is charged with 20.02 g (120.8 mmol) of carbazole, 49.82 g (365.5 mmol) of ZnCl₂, and 300 mL of nitromethane at room temperature. To the resulting dark-brown slurry is added 49.82 g (365.5 mmol) of 2-chloro-2-methylpropane (also known as tertiary-butyl chloride) dropwise from the addition funnel over a period of 2.5 hours. After completing the addition, the resulting slurry is stirred for an additional 18 hours, and the reaction mixture is poured into 800 mL of ice-cold water and extracted with methylene chloride (3×500 mL). The combined extracts are dried with anhydrous magnesium sulfate, filtered, and concentrated, first by rotary evaporation and then by evaporation under high vacuum to remove nitromethane. The resulting residue is dissolved in hot methylene chloride (70 mL), followed by hot hexanes (50 mL), and the resulting solution is cooled to room temperature and then placed in a refrigerator overnight. The resulting solids which formed are isolated, washed with cold hexanes, and then dried under high vacuum to yield 10.80 g (32.0%) of the desired product as off-white crystals. ¹H NMR (400 MHz, CDCl₃) δ 8.11 (d, J=1.6 Hz, 2H), 7.75 (s, 1H), 7.48 (dd, J=8.5, 1.9 Hz, 2H), 7.31 (d, J=8.5 Hz, 2H), 1.48 (s, 18H). ¹³C{¹H} NMR (101 MHz, CDCl₃) δ 142.17 (s), 137.96 (s), 123.45 (s), 123.28 (s), 116.11 (s), 109.97 (s), 34.73 (s), 32.09 (s).

Preparation of 2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenol

To a stirred solution of 10.30 g (50.00 mmol) of 4-(2,4,4-trimethylpentan-2-yl)phenol in 125 mL of methanol at 0° C. is added 7.48 g (50.00 mmol) of NaI and 2.00 g (50.0 mmol) of NaOH. To the resulting mixture is added 86 mL of 5% aqueous NaOCl solution (commercial bleach) over a one hour period. The resulting slurry is stirred for one more hour at 0° C., then 30 mL of aqueous 10% Na₂S₂O₃ solution is added, and the resulting reaction mixture is acidified with the addition of dilute hydrochloric acid. The resulting mixture is extracted with methylene chloride, and the resulting organic layer is washed with brine and then dried over anhydrous magnesium sulfate. The volatiles are removed under vacuum, and the resulting residue is purified by flash chromatography on silica gel, eluting with 5 volume percent (vol %) ethyl acetate in hexanes to yield 11.00 g (66%) of the desired product as a viscous oil. ¹H NMR (CDCl₃) δ 7.60 (d, J=2.5 Hz, 1H), 7.25 (dd, J=8.5 and 2.2 Hz, 1H), 6.90 (d, J=8.5 Hz, 1H), 5.13 (s, 1H), 1.69 (s, 2H), 1.32 (s, 6H) and 0.74 (s, 9H). ¹³C{¹H} NMR (CDCl₃) δ 152.21, 144.52, 135.56, 128.03, 114.17, 85.36, 56.92, 38.01, 32.43, 31.90 and 31.64. GC/MS (m/e): 332 (Mt).

Preparation of 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran

To a stirred solution of 4.91 g (14.8 mmol) of 4-(2,4,4-trimethylpentan-2-yl)phenol and 1.50 g (17.8 mmol) of 3,4-dihydropyran in 5 mL of methylene chloride at 0° C. is added 0.039 g (0.205 mmol) of para-toluenesulfonic acid monohydrate. The resulting solution is allowed to warm to room temperature and stirred thereat for approximately 10 minutes. Then triethylamine (0.018 g, 0.178 mmol) is added, and the resulting mixture is diluted with 50 mL of methylene chloride and successively washed with 50 mL each of 1M NaOH, water, and brine. The organic phase is dried with anhydrous magnesium sulfate, filtered, and concentrated to give a crude material, which is purified by flash chromatography on silica gel using 5 vol % ethyl acetate in hexanes to yield 5.18 g (93.12%) of the desired product as a golden oil. ¹H NMR (CDCl₃) δ 7.74 (d, J=2.3 Hz, 1H), 7.27 (dd, J=2.3 and 8.6 Hz, 1H), 6.99 (d, J=8.6 Hz, 1H), 5.49 (m, 1H), 3.91 (m, 1H), 3.61 (m, 1H), 2.20-1.60 (m, 6H), 1.69 (s, 2H), 1.34 (s, 6H) and 0.75 (s, 9H). ¹³C{¹H} NMR (CDCl₃) δ 153.27, 145.49, 136.98, 127.08, 114.44, 96.72, 87.09, 61.69, 56.91, 37.95, 32.33, 31.81, 31.52, 31.44, 30.26, 25.27, 18.36.

Preparation of 3,6-di-tert-butyl-9-(2-(tetrahydro-2H-pyran-2-yloxy)-5-(2,4,4-trimethyl-pentan-2-yl)phenyl)-9H-carbazole

To a 50-mL, three-necked, round-bottom flask, equipped with a stir bar and condenser, under N2 atmosphere, is added the following: 20 mL of dry toluene; 5.00 g (12.01 mmol) of 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran; 3.56 g (12.01 mmol) of 3,6-di-tert-butyl carbazole; 0.488 g (2.56 mmol) of CuI; 7.71 g (36.2 mmol) of K₃PO₄; and 0.338 g (3.84 mmol) of N,N′-dimethylethylenediamine. The resulting reaction mixture is heated, under reflux, for 48 hours, cooled, and filtered through a bed of silica gel. The silica gel is rinsed with tetrahydrofuran (“THF”), and the resulting solution is concentrated to give a crude residue. Purification is accomplished by recrystallization from acetonitrile, to yield 4.57 g (67.0%) of the desired product as a white solid. ¹H NMR (CDCl₃) δ 8.13 (t, J=1.71 Hz, 1H), 7.48 (d, J=2.4 Hz, 1H), 7.40 (m, 3H), 7.31 (d, J=8.68 Hz, 1H), 7.14 (d, J=8.68 Hz, 1H), 7.08 (d, J=8.56 Hz, 1H), 5.22 (t, J=2.81 Hz, 1H), 3.72 (td, J=11.12 and 2.8 Hz, 1H), 3.47 (dt, J=11.12 and 3.47 Hz, 1H), 1.75 (s, 2H), 1.474 (s, 9H), 1.472 (s, 9H), 1.394 (s, 3H), 1.391 (s, 3H), 1.37-1.12 (m, 6H), 0.82 (s, 9H). ¹³C{¹H} NMR (CDCl₃) δ 150.96, 144.22, 142.07, 140.02, 127.49, 126.60, 126.56, 123.14, 123.12, 122.96, 116.37, 115.88, 115.72, 110.18, 109.52, 97.02, 61.56, 57.03, 38.23, 34.69, 32.41, 32.07, 31.86, 31.72, 31.50, 29.98, 25.06, 17.61.

Preparation of 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole

To a stirred solution of 2.5 g (4.4 mmol) of carbazole derivative in 40 mL of THF at 0° C. under nitrogen atmosphere 2.8 mL (7.0 mmol) of n-butyl lithium (2.5 M solution in hexanes) is added over a period of 5 minutes. The solution is stirred at 0° C. for 3 hours. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.44 mL, 7.0 mmol) is added to this, and the stirring continued at 0° C. for 1 more hour. The reaction mixture is slowly warmed to room temperature and stirred for 18 hours. The reaction mixture is concentrated to dryness by rotary evaporation, and 100 mL of ice-cold water is added. The mixture is extracted with methylene chloride. The organic layer is washed with brine and dried over anhydrous magnesium sulfate. Removal of the solvent, followed by recrystallization from acetonitrile, gives 2.4 g (78.6%) of titled product as white solid. ¹H NMR (CDCl₃) δ 8.30-7.96 (m, 2H), 7.81 (d, J=2.5 Hz, 1H), 7.58-7.32 (m, 3H), 7.14 (d, J=8.6 Hz, 2H), 4.85 (d, J=2.8 Hz, 1H), 2.76 (td, J=11.0, 2.7 Hz, 1H), 2.59 (dd, J=7.9, 3.5 Hz, 1H), 1.73 (s, 2H), 1.67-0.87 (m, 6H), 1.46 (s, 9H), 1.45 (s, 9H), 1.38 (s, 9H), 1.37 (s, 9H), 0.78 (s, 9H); ¹³C{¹H} NMR (CDCl₃) δ 156.25, 145.86, 142.05, 142.01, 139.79, 139.78, 133.82, 130.61, 129.72, 123.39, 123.37, 123.05, 115.59, 115.55, 110.20, 110.11, 101.41, 83.64, 61.20, 56.95, 38.37, 34.68, 32.42, 32.08, 31.90, 31.45, 29.97, 25.06, 25.04, 24.79, 18.16. MS m/e 716.38 (M+Na).

Preparation of 2′,2′″-(((-cyclohexane-1,2-diyl)bis(methylene))bis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1,1′-biphenyl]-2-ol)

The borylated fragment (25.0 g, 36.0 mmol) and (trans)-1,2-bis((2-bromophenoxy)methyl)cyclohexane (7.365 g, 16.21 mmol) is dissolved in 200 mL of toluene. NaOH (4.32 g, 108.10 mmol) is dissolved in 22 mL of water and this solution is added to the toluene solution. The resulting mixture is purged with nitrogen for 15 minutes. Pd(PPh₃)₄ (833 mg, 0.72 mmol) is taken from a dry box and added dry under a positive stream of nitrogen to the toluene solution. The reaction mixture is then heated under reflux for 48 hours. The organic layer is separated and washed with 100 mL of water and 50 mL of a saturated NaCl solution and then dried over MgSO₄. The resulting organic solution is then passed through a silica gel pad and then dried under vacuum. THF (25 mL), methanol (25 mL), and concentrated HCl (1 mL) are added and the solution is heated under reflux for one hour. The reaction is then cooled to room temperature and water (100 mL) and diethyl ether (100 mL) are added. The organic layer is separated and dried over MgSO₄. The volatiles are removed under vacuum. This crude residue is purified by recrystallization from diethyl ether and methanol, furnishing the desired product as a white solid (18.2 g, 89% yield). ¹H NMR (400 MHz, C₆D₆) δ 8.41-8.35 (m, 2H), 7.59-7.30 (m, 7H), 7.03-6.94 (m, 1H), 6.89 (td, J=7.5, 1.1 Hz, 1H), 6.40 (d, J=8.3 Hz, 1H), 5.97 (s, 1H), 3.59 (dd, J=9.9, 2.8 Hz, 1H), 3.40 (d, J=9.5 Hz, 1H), 1.57 (s, 2H), 1.54-1.49 (m, 1H), 1.42 (d, J=5.3 Hz, 20H), 1.25 (s, 6H), 1.002H), 0.85 (s, 9H). 2H), 0.85 (s, 9H).

Preparation of Catalyst-2

Inside a drybox, a jar was charged with ZrCl₄ (0.988 g, 4.24 mmol) and toluene (100 mL), and was placed in a freezer to cool to −35° C. Once cool, it was removed, and MeMgBr (6.40 mL of a 3M solution in Et₂O, 19.5 mmol) was added. The resulting suspension was stirred for 3 minutes, at which point the bis-biphenylphenolic ligand (5.34 g, 4.24 mmol) was added. The mixture was allowed to warm to room temperature and was stirred for 18 hours, then filtered and the filtrate was collected and dried under vacuum. The resulting residue was washed with cold hexane (50 mL) and filtered. The insoluble material was collected, and suspended in methylcyclohexane (200 mL) and filtered. The filtrate was dried, affording catalyst-2 as a mixture of isomers (˜2:1 ratio) (4.41 g, 75%). ¹H NMR (400 MHz, C₆D₆) δ 8.66 (d, J=1.8 Hz), 8.40 (d, J=1.9 Hz), 7.75-7.55 (m), 7.48-7.20 (m), 6.95-6.70 (m), 5.31-5.07 (m), 5.04-4.79 (m), 4.61-4.28 (m), 3.96 (d, J=10.8 Hz), 3.46 (d, J=12.3 Hz), 1.55 (s), 1.53 (s), 1.35-1.31 (m), 1.28 (s), 1.27 (s), 0.91 (s), 0.85 (s), −0.80 (s), −0.88 (s).

The cocatalyst is modified methylaluminoxane, MMAO-3A solution in heptane, which is commercially available from Akzo Nobel N.V., Amsterdam, Netherlands.

EXAMPLES Example 1

Prepare three Samples (S1-S3) according to the following procedure. S1 and S2 are ethylene/propylene copolymers, while S3 is an ethylene/octene copolymer. Continuous solution polymerizations are carried out using two, computer-controlled, continuous stirred tank reactors (CSTR's) connected in series and configured in a single or dual reactor configuration. Each 5-liter reactor is hydraulically full and set to operate at steady state conditions. The effluent from the first reactor (R-1) feeds into the second reactor (R-2). Otherwise, the two reactors are operated independently. Purified Isopar®E, ethylene, propylene, and hydrogen (where used) are supplied to the reactor through mass-flow controllers using variable speed diaphragm pumps that control the flow rates and reactor pressure. The desired temperature is maintained and monitored using an internal thermocouple. At the discharge of the pump, a side stream is taken to provide flush flows for the catalyst, cocatalyst, and injection lines and the reactor agitator. A slight excess of cocatalyst is used. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by the manual adjustment of needle valves. The remaining solvent is combined with propylene, ethylene, and/or optionally, a diene, and hydrogen (where used) and fed to the reactor. A mass flow controller is used to deliver hydrogen to the reactor as needed. The temperature of the solvent/monomer solution is controlled by use of a heat exchanger before entering the reactor. The catalyst is fed to the reactor separately from the cocatalyst. The component solutions are metered using pumps and mass flow meters and are combined with the catalyst flush solvent and introduced into the bottom of the reactor. The reactor is run liquid-full at 410 psig (2.82 MPa) with vigorous stirring. Product is removed through exit lines at the top of the reactor. Polymerization is stopped by the addition of a small amount of water into the exit line along with any stabilizers or other additives. Solvent is then removed and the product is recovered using a devolatilizing extruder and water-cooled pelletizer.

The ethylene interpolymers are prepared using two continuous stirred tank reactors connected in series. Sample S3 is prepared by flowing monomers, solvent, catalyst-1, and cocatalyst to the first reactor according to the process conditions outlined in Table 1; no subsequent reactor is employed for S3. To prepare samples Si and S2, the first reactor contents as described in Table 1 are flowed to a second reactor in series. Additional catalyst-1 and cocatalyst are added to the second reactor, as well as a small amount of MMAO as a scavenger.

TABLE 1 Reactor Process Conditions for Preparing Samples S1-S3 Parameter Unit S1 S2 S3 First Reactor I₂ (@190) g/10 min 2.08 1.28 1.61 I₁₀ (@190) g/10 min 29.35 22.43 19.92 I₁₀/I₂ 14.11 17.52 12.37 Density g/cm³ 0.8856 0.8904 0.8869 Solvent kg/hr 12.4 15.7 22.1 Ethylene kg/hr 1.76 2.2 3.06 Hydrogen mL/min 36 47 48 1-Octene kg/hr 1.45 Propylene kg/hr 0.8 0.7 Feed Temperature ° C. 9 5.2 Solvent/Ethylene Ratio kg/kg 7.5 7.5 7.7 Reactor Temperature ° C. 140 140 140 Delta T ° C. 0 −1.29 0.09 Oilbath ° C. 114 104.9 124 Catalyst Type Catalyst-1 Catalyst-1 Catalyst-2 Catalyst Concentration mg/kg 0.2 0.4 0.4 Catalyst Flow g/hr 152 73 184 Catalyst Efficiency kg/mg 0.72 0.93 0.58 Cocatalyst Concentration mmol/kg 25 64 64 Cocatalyst Flow g/hr 122 97 247 Ethylene Conversion % 92.7 91.8 93.4 Ethylene g/l 5.3 6.2 5 Viscosity cPa 738 764 133 Second Reactor Solvent kg/hr 12.3 15.7 — Ethylene kg/hr 2.6 2.04 — Hydrogen mL/min 400 615 — Propylene kg/hr 0.93 0.75 — Feed Temperature ° C. 6.4 8.1 — Solvent/Ethylene Ratio kg/kg 5.07 8.06 — Reactor Temperature ° C. 159 160.1 — Delta T ° C. −1.05 0.25 — Oilbath ° C. 130.7 149.4 — Catalyst Type Catalyst-1 Catalyst-1 — Catalyst Concentration mmol/kg 0.3 0.4 — Catalyst Flow g/hr 335 216 — Catalyst Efficiency kg/mg 0.32 0.31 — Cocatalyst Concentration mmol/kg 25 64 — Cocatalyst Flow g/hr 495 420 — Ethylene Conversion % 91.7 90.1 — Ethylene g/l 7.7 6.5 — Viscosity cPa 77.8 43.9 —

Analyze S1-S3 according to the above-described Test Methods. Two additional Samples (S4 and S5) are also analyzed, along with four Comparative Samples (CS1-CS4). S4 is VISTALON™ 722 EP, and S5 is VISTALON™ 1703 P EPDM, each described above. CS1 is NORDEL™ IP 3722P EL EPDM, CS2 is POE-1, CS3 is POE-2, and CS4 is LDPE-1, all as described in the Materials section, above. The results are provided in Table 2, below.

TABLE 2 Properties of S1-S5 and CS1-CS4 S1 S2 S3 S4 S5 CS1 CS2 CS3 CS4 Density 0.885 0.890 0.888 0.867 0.879 0.872 0.880 0.874 0.921 (g/cm³) I₂ (g/10 2.4 1.5 1.7 1.0 <0.1 0.7 2.7 4.3 1.7 min.) Melt 3.5 3.2 3.5 3.8 19.0 7.0 1.6 0.8 8.4 Strength (cN) at 190 ° C. Melt Strength N/A 6.4 8.3 N/A N/A N/A 5.4 3.1 16.4 (cN) at 135° C. Mw/Mn 3.9 4.3 2.5 2.7 10.4 3.2 2.3 2.3 4.9 V0.1/V100 13 20 9 12 76 33 4 3 17 at 190° C. V100 (Pa · s) 606 654 836 928 1024 1514 963 825 579 at 190° C. V0.1/V100 N/A 36 18 N/A N/A N/A 5 3 38 at 135° C. V100 (Pa · s) N/A 1146 1646 N/A N/A N/A 2067 1530 985 at 135° C. Zero Shear Not 38110 31190 Not Not Not Not Not 31750 Viscosity at Available Available Available Available Available Available 135° C. (Pa s)

Analyze the extrusion characteristics of samples S2, S3, CS1, CS2, and CS4 according to the procedures outlined in the Test Methods section, above. The results are provided in Table 3, below.

TABLE 3 Extrusion Characteristics of S2, S3, CS1, CS2, and CS4 S2 S3 CS1 CS2 CS4 Melt Discharge Temperature During Extrusion (° C.) 25 rpm 120.0 129.4 129.4 132.2 121.1 50 rpm 136.7 146.1 157.8 153.3 133.3 75 rpm 146.1 163.9 184.4 173.9 141.1 100 rpm  154.4 177.2 207.8 192.2 148.3 Extrusion Rate (lb/hr) 25 rpm 49.6 49.9 49.0 50.5 42.8 50 rpm 99.0 100.2 99.4 101.4 89.4 75 rpm 150.6 149.4 150.0 153.6 140.4 100 rpm  201.0 198.6 201.0 207.6 192.6 Extrusion Rate at Melt Discharge Temperature of 145° C. (lb/hr) 145 97 77 81 168

Looking at the data presented in Tables 2 and 3, S1 to S5 exhibit the following properties which are desirable for formulated power cable insulations: low viscosities at 100 s⁻¹ (V100), high shear thinning (V0.1/V100), high zero-shear viscosities, and low densities (for more flexible compositions). The good melt rheological characteristics of S2 and S3 result in sufficiently low melt discharge temperatures during extrusion at screw speeds up to 100 rpm. In contrast, CS1 and CS2 show much higher melt discharge temperatures during extrusion. Additionally, whereas CS4 did process well during extrusion, its density is unacceptably high. A lower melt discharge temperature is considered desirable so as to avoid premature crosslinking during extrusion of insulation compounds containing peroxides. Consequently, the extrusion rates corresponding to a melt discharge temperature of 145° C. (close to the maximum practiced industrially with compositions containing dicumyl peroxide) were relatively greater with the examples of this invention (versus CS1 and CS2).

Example 2

Prepare eight inventive insulation compositions, S6-S13, and five comparative insulation compositions, CS5-CS9, using the polymers of S1-S5 and CS1-CS4 according to the following method and using the formulations provided in Table 4, below. Melt the dicumyl peroxide by heating to 60° C. then mix with the Nofmer MSD at a 5:1 ratio (of peroxide to Nofmer MSD). Prepare a “solids” mixture by mixing everything (except peroxide and Nofmer MSD) in a container by hand. Next, compound the solids mixture in a 250-cm³ Brabender batch mixer with cam rotors at 190° C. and 40 rpm for 5 minutes. The resulting blend is removed from the mixer, cold pressed into a thin sheet, cut into strips, and fed through a pelletizer to make pellets. The polymer pellets are heated in a glass jar at 60° C. for 2 hours and subsequently sprayed with the stipulated amount of peroxide/Nofmer MSD mixture using a syringe. The jar is tumble-blended for 10 minutes at room temperature and heated at 50° C. for 16 hours. Next, the contents of the jar are mixed in a 250-cm³ Brabender mixing bowl with cam rotors at 120° C. and 30 rpm for 10 minutes (after loading).

The compositions are subsequently tested in a moving die rheometer at 140° C. or 182° C. for evaluation of crosslinking characteristics. For melt rheological measurements, the compositions are compression molded at the following conditions to prevent significant crosslinking: 500 psi (3.5 MPa) at 120° C. for 3 minutes, followed by 2500 psi (17 MPa) at this temperature for 3 minutes, cooling to 30° C. at this pressure, and opening the press to remove the molded plaque. For electrical and mechanical measurements, the compositions are compression molded at the following conditions to make completely crosslinked specimens of different dimensions: 500 psi (3.5 MPa) at 125° C. for 3 minutes, followed by 2500 psi (17 MPa) at 180° C. for 20 minutes, cooling to 30° C. at this pressure, and opening the press to remove the molded plaque. Analyze each of S6-S13 and CS5-CS9 according to the procedures provided in the Test Methods section, above. Results are provided in Table 4, below.

TABLE 4 Compositions and Properties of S6-S13 and CS5-CS9 S6 S7 S8 S9 S10 S11 S12 S13 CS5 CS6 CS7 CS8 CS9 Composition (wt %) EP Polymer of S1 97.01 88.23 EP Polymer of S2 96.48 97.08 EO Polymer of S3 96.48 97.08 EP Polymer of S4 97.01 EPDM Polymer of 97.01 S5 EPDM Polymer of 97.01 CS1 EO Polymer of 97.01 CS3 LDPE of CS4 97.01 96.48 97.08 Polypropylene 8.78 Dicumyl Peroxide 1.80 2.00 1.50 2.00 1.50 1.80 1.80 1.80 1.80 1.80 1.80 2.00 1.50 PEG 20000 0.29 0.58 0.58 0.58 0.58 0.29 0.29 0.29 0.29 0.29 0.29 0.58 0.58 Lowinox TBM-6 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 Sabostab UV 119 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Nofmer MSD 0.36 0.40 0.30 0.40 0.30 0.36 0.36 0.36 0.36 0.36 0.36 0.40 0.30 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Properties V0.1/V100 26.6 NA NA NA NA 29.8 33.0 104.6 57.8 8.9 43.9 NA NA (120° C.) V100 at 120° C. 921 NA NA NA NA 1120 1160 1130 1750 1540 617 NA NA (Pa · s) Extensional 442890 NA NA NA NA 1752000 696370 3512800 1374400 414680 760430 NA NA Viscosity at 120° C., 1 s⁻¹, and Hencky Strain of 1 (Poise) V0.1/V100 NA 51.4 43.9 36.7 28.4 NA NA NA NA NA NA 48.9 48.4 (135° C.) V100 at 135° C. NA 960 1022 1001 914 NA NA NA NA NA NA 553 644 (Pa · s) Extensional NA 471740 482940 539450 572580 NA NA NA NA NA NA 577030 539110 Viscosity at 135° C., 1 s⁻¹, and Hencky Strain of 1 (Poise) Maximum NA 1339400 1341100 1742900 1976600 NA NA NA NA NA NA 5246500 4515700 Extensional Viscosity at 135° C., 1 s⁻¹ (Poise) Zero Shear NA 40510 34950 27480 28510 NA NA NA NA NA NA 27130 32560 Viscosity at 135° C. (Pa · s) MDR: ts1 at 54.6 45.5 67.9 29.0 43.7 43.3 38.1 36.4 31.6 28.5 67.6 61.1 112.9 140° C. (minutes) MDR: ML at 0.14 0.20 0.20 0.22 0.22 0.14 0.26 0.36 0.34 0.10 0.18 0.18 0.18 182° C. (lb in) MDR: MH-ML at 3.9 3.4 2.1 5.4 3.7 3.4 6.3 5.8 5.2 5.7 3.0 3.0 1.8 182° C. (lb in) Gel content (wt %) 76 68 52 89 78 77 90 95 87 97 84 83 75 after crosslinking Hot creep at 41 72 NM 31 89 34 18 14 23 19 35 61 NM 200° C., 0.2 MPa (%) after crosslinking Dissipation Factor 5.40 0.27 0.23 7.62 4.37 3.02 7.71 0.19 2.67 0.13 0.09 0.08 0.07 at 2 kV, 130° C., 60 Hz (%) after crosslinking ACBD, unaged 33.8 36.2 36.6 35.9 36.2 33.4 32.5 32.8 34.3 33.6 35.6 36.7 36.9 (kV/mm) ACBD, aged 30.8 32.6 33.9 35.5 34.9 29.9 31.1 29.0 31.2 31.3 28.7 36.7 36.5 (kV/mm) Hardness (Shore 29.9 27.5 23.2 29.2 29.7 31.6 15.6 23.8 24.2 26.2 48.9 44.5 43.4 D) after crosslinking Hardness (Shore 88.0 84.2 86.8 83.7 85.6 89.2 65.1 77.7 80.8 81.9 95.3 95.7 96.8 A) after crosslinking Flexural Modulus, NA 51.5 53.3 42.8 45.1 NA NA NA NA NA NA 151.7 166.3 2% Secant (MPa) after crosslinking NM: Not measurable (not enough crosslinking for hot creep to be measurable) NA: Not available

The data provided in Table 4 show that S6-S13 exhibit satisfactory melt rheological properties (at temperatures of 120° C. or 135° C., representative of extrusion conditions), crosslinking characteristics, electrical properties, and mechanical properties. Compared with the relatively soft comparative samples (CS5 and CS6), the values of “V100 at 120° C.” indicated for S6-S13 are desirably lower. In comparison with CS7-CS9, the compositions of S6-S13 are much softer.

Example 3

Prepare three Comparative Samples (CS10-CS12) according to the following procedure and the formulations provided in Table 5, below. The compositions are first compounded without peroxide in a 250-cm³ Brabender batch mixer with cam rotors at 140° C. and 35 rpm for 5 minutes. The melt blended samples are removed from the mixing bowl and transferred to a roll mill where peroxide is added at 115° C. and mixed for 5 minutes. The compositions removed from the roll mill are compression molded to various thicknesses at 500 psi (3.5 MPa) pressure and 125° C. for 3 minutes, followed by 2500 psi (17 MPa) pressure for 15 minutes at 180° C. to complete crosslinking. The press is then cooled to 30° C. at 2500 psi pressure. Once at 30° C., the press is opened and the plaques are removed.

TABLE 5 Compositions of CS10-CS12 CS10 CS11 CS12 EPDM Polymer of CS1 64.7 53.4 54.4 Burgess KE clay 32.4 32.4 32.4 LDPE-2 — 2.7 2.7 Zinc Oxide — 2.7 2.7 Polydispersion ERD-90 — 2.7 2.7 Antilux 654 Parafin Wax — 1.9 1.9 FlowSperse PAC-473 — 1.4 1.4 Agerite MA 0.34 0.34 — Cyanox 2212 — — 0.34 Dicumyl Peroxide 2.5 2.5 1.5 Total 100 100 100

Analyze CS10-CS12 according to the procedures provided in the Test Methods section, above. Results are provided in Table 6, below.

TABLE 6 Properties of CS10-CS12 CS10 CS11 CS12 MDR: ts1 at 140° C. (minutes) 5.6 4.6 >90 MDR: ML at 182° C. (lb in) 0.90 N/A 0.91 MDR: MH-ML at 182° C. (lb in) 22.05 N/A 1.0 Gel content (wt %) after crosslinking 98 95 N/A Hot creep at 200° C., 0.2 MPa (%) after 4 2 NM crosslinking Dissipation Factor at 2 kV, 130° C., 60 Hz (%) 0.72 0.86 0.93 after crosslinking Hardness (Shore D) after crosslinking 24.2 26.5 N/A Hardness (Shore A) after crosslinking 81.4 84.9 85.4 NM: Not measurable (not enough crosslinking for hot creep to be measurable)

Looking at the data provided in Table 6, above, note that CS10-CS12 are clay-filled compositions made with the EPDM polymer of CS1, which has V100 at 190° C. of 1514 Pa·s (i.e., >1200 Pa·s). Since CS10-CS12 employ the same polymer as CS5 (which did not contain any filler), it is reasonable to suppose that the V100 at 120° C. of CS10-CS12 would be greater than that of CS5, which is not desirable from an extrusion perspective. Furthermore, the ts1 at 140° C. values of CS10 and CS11 are less than 10 minutes (unlike Samples S6 to S13, which all exhibited values of ts1 at 140° C. that are well above 10 minutes), which indicates relatively greater propensity for “scorch” (premature crosslinking) during extrusion.

Example 4

Prepare six additional Samples (S14-S19) and four additional Comparative Samples (CS13-CS16) using the preparation method described in Example 2, above (except that the “strips” were cooled in a freezer to harden before being fed through a pelletizer to make pellets), and the formulations provided in Table 7, below. Evaluate S14-S19 and CS13-CS16 according to the procedures outlined in the Test Methods section, above. Results are provided in Table 7, below.

TABLE 7 Compositions and Properties of S14-S19 and CS13 to CS16 S14 S15 S16 S17 S18 S19 CS13 CS14 CS15 CS16 Composition (wt %) EP Polymer of S2 96.48 62.71 87.80 96.48 EO Polymer of S3 96.48 62.71 EPDM of CS1 96.48 EO Polymer of CS3 96.48 LDPE-1 of CS4 33.77 33.77 96.48 96.48 Polypropylene 8.68 Dicumyl Peroxide 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 PEG 20000 0.58 0.58 0.58 0.58 0.58 0.58 0.58 0.58 0.58 0.58 Lowinox TBM-6 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 0.34 Sabostab UV 119 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Nofmer MSD (AMSD) 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Properties V0.1/V100 at 135° C. 51.5 54.1 58.1 34.9 42.3 49.5 52.6 45.7 86.2 13.2 V100 at 135° C. (Pa · s) 805 790 1220 1440 1051 960 821 823 1163 1194 Extensional Viscosity 409690 496460 696850 536050 554620 2.88E+05 445160 2.96E+05 5.21E+05 39788 at 135° C., 1 s⁻¹ and Hencky Strain of 1 (Poise) Maximum Extensional 920440 2493200 794590 17885000 3314200 3.51E+05 2964300 3.58E+05 6.28E+05 1.71E+05 Viscosity at 135° C., 1 s⁻¹ (Poise) Hencky Strain 2.8 3.8 0.7 3.7 3.7 0.6 3.5 0.7 0.7 0.3 at Maximum Extensional Viscosity Zero Shear Viscosity 35400 33710 49690 26490 41830 31410 47700 30340 70770 7581 at 135° C. (Pa s) MDR: ts1 at 140° C. 52.7 51.4 38.4 31.6 37.1 51.8 61.3 58.3 31.6 37.4 (minutes) MDR: ML at 182° C. 0.19 0.20 0.19 N/A 0.20 0.18 0.17 0.17 0.31 0.08 (lb in) MDR: MH-ML 3.23 3.25 2.69 N/A 4.42 3.35 3.17 3.26 5.16 4.91 at 182° C. (lb in) Gel content (wt %) after 62.7 71.0 65.2 89.1 85.4 71.5 81.7 80.4 83.3 90.3 crosslinking Hot creep at 200° C., 125 76 Not 32 37 62 56 42 35 42 0.2 MPa (%) Available after crosslinking Dissipation Factor at 2 kV, 1.24 0.87 0.49 8.66 4.53 0.65 0.16 0.18 0.24 0.81 130° C., 60 Hz (%) after crosslinking Hardness (Shore D) after 29.2 36.3 31.2 31.8 36.0 29.5 43.4 48.4 18.1 19.3 crosslinking Hardness (Shore A) after 87.1 90.9 88.8 85.7 90.5 86.4 96.1 94.7 70.2 72.1 crosslinking Flexural Modulus, 2% 50.6 74.7 64.2 44.7 74.8 52.3 161.6 167.4 17.7 23.2 Secant (MPa) AC Breakdown Strength- 36.2 36.7 36.6 36.7 36.5 35.5 37.0 36.2 35.4 34.5 unaged (kV/mm) AC Breakdown 34.2 35.8 36.0 33.8 36.0 33.1 32.4 34.6 29.6 30.7 Strength-aged (kV/mm)

The compositions of S14 to S19 exhibit satisfactory melt rheological properties (at a temperature of 135° C., representative of extrusion conditions), crosslinking characteristics, electrical properties, and mechanical properties.

Example 5

Prepare one additional Sample (S20) and two additional Comparative Samples (CS17-CS18) using the preparation method described in Example 2, above (except that the “strips” were cooled in a freezer to harden before being fed through a pelletizer to make pellets), and the formulations provided in Table 8, below. Evaluate S20 and CS17-CS18 according to the procedures outlined in the Test Methods section, above. Results are provided in Table 8, below.

TABLE 8 Compositions and Properties of S20 and CS17 to CS18 S20 CS17 CS18 Composition (wt %) EP Polymer of S2 64.08 EPDM Polymer of CS1 64.08 EO Polymer of CS3 64.08 Translink 37 calcined clay 32.40 32.40 32.40 Dicumyl Peroxide 2.00 2.00 2.00 PEG 20000 0.58 0.58 0.58 Lowinox TBM-6 0.34 0.34 0.34 Sabostab UV 119 0.20 0.20 0.20 Nofmer MSD (AMSD) 0.40 0.40 0.40 Total 100.00 100.00 100.00 Properties V0.1/V100 at 135° C. 75.9 86.8 19.7 V100 at 135° C. (Pa · s) 1463 2238 2255 Extensional Viscosity at 135° C., 4.47E+05 8.21E+05 62595 1 s⁻¹ and Hencky Strain of 1 (Poise) Maximum Extensional Viscosity at 6.28E+05 1.06E+06 3.24E+05 135° C., 1 s⁻¹ (Poise) Hencky Strain at Maximum 0.7 0.7 0.3 Extensional Viscosity Zero Shear Viscosity at 135° C. 57310 141500 18210 (Pa s) MDR: ts1 at 140° C. (minutes) 25.3 18.9 21.2 MDR: ML at 182° C. (lb in) 0.35 0.60 0.15 MDR: MH-ML at 182° C. (lb in) 8.75 11.53 11.71 Gel content (wt %) after crosslinking 75.5 88.0 92.3 Hot creep at 200° C., 0.2 MPa (%) 11 5 10 after crosslinking Dissipation Factor at 2 kV, 130° C., 2.07 2.09 3.46 60 Hz (%) after crosslinking Hardness (Shore D) after crosslinking 34.1 22.8 25.8 Hardness (Shore A) after crosslinking 90.3 79.2 81.1 Flexural Modulus, 2% Secant (MPa) 104.8 28.5 36.3 AC Breakdown Strength - unaged 36.6 34.2 34.3 (kV/mm) AC Breakdown Strength - aged 35.0 33.1 31.9 (kV/mm)

The composition of S20 exhibits satisfactory melt rheological properties (including comparatively lower V100) at a temperature of 135° C. (representative of extrusion conditions), crosslinking characteristics, electrical properties, and mechanical properties. 

The invention claimed is:
 1. A crosslinkable polymeric composition comprising: (a) 10 to 89 weight percent, based on the total weight of said crosslinkable polymeric composition, of an ethylene-based interpolymer having the following properties: (i) a density of 0.93 g/cm³ or less, (ii) a high-shear viscosity (V100) at 190° C. and 10% strain of 1,200 Pas or less, (iii) a shear thinning ratio (V0.1/V100) at 190° C. and 10% strain of at least 8, and (iv) a melt index (I₂) greater than 1 g/10 minutes; and (b) 10 to less than 90 weight percent, based on the total weight of said crosslinkable polymeric composition, of a filler; and wherein said ethylene-based interpolymer is not prepared in a high-pressure reactor or process.
 2. The crosslinkable polymeric composition of claim 1, wherein said crosslinkable polymeric composition is rendered crosslinkable by further comprising (c) an organic peroxide in an amount of at least 0.5 weight percent based on the total weight of said crosslinkable polymeric composition.
 3. The crosslinkable polymeric composition of claim 1, wherein said ethylene-based interpolymer is an interpolymer selected from an ethylene/propylene copolymer, an ethylene/1-octene copolymer, and an ethylene/propylene/diene comonomer terpolymer.
 4. The crosslinkable polymeric composition of claim 1, further comprising a high-pressure polyethylene in an amount up to 80 weight percent based on the entire weight of the crosslinkable polymeric composition.
 5. The crosslinkable polymeric composition of claim 1, further comprising a propylene polymer in an amount up to 80 weight percent based on the entire weight of the crosslinkable polymeric composition.
 6. The crosslinkable polymeric composition of claim 1, wherein said filler is selected from the group consisting of heat-treated clay, surface-treated clay, and organoclay.
 7. The crosslinkable polymeric composition of claim 1, wherein said crosslinkable polymeric composition has one or more of the following properties: (a) a zero shear viscosity at 135° C. of at least 10,000 Pas; (b) an extensional viscosity of greater than 300,000 Poise when measured at 120° C. or 135° C., 1 s⁻¹, and a Hencky strain of 1; and (c) a ts1 at 140° C. of at least 10 minutes.
 8. A crosslinked polymeric composition prepared from the crosslinkable polymeric composition of claim
 1. 9. The crosslinked polymeric composition of claim 8, wherein said crosslinked polymeric composition has one or more of the following properties: (a) an MH-ML at 182° C. of at least 0.2 lb-in; (b) a shore D hardness of 40 or less; (c) a shore A hardness of 93 or less; (d) a gel content of at least 30%; (e) a hot creep value of 200% or less; and (f) a dissipation factor of less than 10% when measured at 60 Hz, 2 kV, and 130° C.
 10. A coated conductor comprising: (a) a conductor; and (b) an insulation layer at least partially surrounding said conductor, wherein at least a portion of said insulation layer is formed from at least a portion of said crosslinked polymeric composition of claim
 9. 11. The crosslinkable polymeric composition of claim 3, wherein said ethylene-based interpolymer is an ethylene/1-octene copolymer. 